Microbicidal benzotriazole compounds

ABSTRACT

Novel benzotriazolesulfonic acid derivatives of formula ##STR1## wherein: R 1  is hydrogen, halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy having at least two identical or different halogen atoms, CF 3 , nitro or the group N(R&#39;)R&#34;, wherein R&#39; and R&#34; are each independently of the other C 1  -C 4  alkyl; 
     R 2  is phenoxy or phenylthio each of which is unsubstituted or mono- to tri-substituted by halogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, C 1  -C 4  haloalkoxy having at least two identical or different halogen atoms, cyano, nitro, C 2  -C 4  alkenyl, C 2  -C 4  alkynyl, phenyl, 2-phenylethynyl or by a further phenoxy radical that is unsubstituted or substituted by halogen, C 1  -C 4  alkyl and/or by C 1  -C 4  alkoxy; or R 2  is the radical O--CH 2  --O; 
     R 3  is alkyl, aryl or aralkyl having a maximum of 14 carbon atoms, these radicals can be substituted by halogen, C 1  -C 4  alkyl and/or by nitro; 
     including the position isomers of R 1  and R 2 , insofar as those substituents occupy positions 5 and 6. 
     The novel compounds have plant-protecting properties and are suitable especially for protecting plants against attack by phytopathogenic microorganisms such as fungi, especially Oomycetes.

This application is a divisional of Ser. No. 07/931,884, filed Aug. 18,1992, now abandoned, which is a continuation of Ser. No. 07/717,751,filed Jun. 19, 1991, now abandoned.

The present invention relates to novel benzotriazolesulfonic acidderivatives of the following formula I. It relates furthermore to thepreparation of those compounds and to agrochemical compositions thatcomprise at least one of those compounds as active ingredient. Theinvention also relates to the preparation of the said compositions andto the use of the compounds or compositions for controlling orpreventing an attack on plants by phytopathogenic microorganisms,especially fungi.

The compounds according to the invention correspond to the generalformula I ##STR2## wherein: R₁ is hydrogen, halogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₄ haloalkoxy having at least two identical or differenthalogen atoms, CF₃, nitro or the group N(R')R", wherein R' and R" areeach independently of the other C₁ -C₄ alkyl;

R₂ is phenoxy or phenylthio each of which is unsubstituted or mono- totri-substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy having at least two identical or different halogen atoms,cyano, nitro, C₂ -C₄ alkenyl, C_(2-C) ₄ alkynyl, phenyl,

2-phenylethynyl or by a further phenoxy radical that is unsubstituted orsubstituted by halogen, C₁ -C₄ alkyl and/or by C₁ -C₄ alkoxy; or R₂ isthe radical O--CH₂ --O;

R₃ is alkyl, aryl or aralkyl having a maximum of 14 carbon atoms, theseradicals can be substituted by halogen, C₁ -C₄ alkyl and/or by nitro;

including the position isomers of R₁ and R₂, insofar as thosesubstituents occupy positions 5 and 6.

Depending on the number of carbon atoms indicated, alkyl on its own oras a component of another substituent, such as alkoxy or haloalkoxyetc., is to be understood as being, for example, the followingstraight-chain or branched groups: methyl, ethyl, propyl, butyl andtheir isomers, for example isopropyl, isobutyl, tert-butyl etc. Halogenand halo are fluorine, chlorine, bromine or iodine. Haloalkoxy istherefore a mono-to per-halogenated alkoxy radical, for example OCH₂ F,OCHF₂, OCHFCH₃, OCH₂ CH₂ Br, OCF₂ CHFCl etc. C₂ -C₄ alkenyl is anunsaturated aliphatic radical having one or more double bonds, forexample propen-1-yl, allyl, buten-1-yl, buten-2-yl, buten-3-yl, etc.Alkynyl is to be understood as being unsaturated aliphatic radicalshaving a maximum of 4 carbon atoms, for example propargyl, butyn-2-yl,butyn-3-yl etc. Aryl and aralkyl are, for example, phenyl, benzyl,phenethyl, naphthyl etc.

The compounds of formula I are oils or solids that are stable at roomtemperature and are distinguished by valuable microbicidal properties.They can be used preventively and curatively in the agricultural sectoror related fields for controlling plant-destructive microorganisms. Thecompounds of formula I according to the invention are, when used at lowconcentrations, distinguished not only by excellent microbicidal,especially fungicidal, activity, but also by especially good planttolerability.

The following groups of compounds are preferred on account of theirpronounced plant-protecting properties:

Compounds of formula I wherein:

1a)

R₁ is hydrogen, halogen, C₁ -C₄ alkyl, methoxy, ethoxy, CF₃, NO₂, C₁ -C₂haloalkoxy having at least two fluorine atoms, diethylamine ordimethylamine;

and R₂ and R₃ are as defined for formula I.

1b)

R₁ is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy,CF₃, NO₂, C₁ -C₂ haloalkoxy having at least 2 fluorine atoms, ordimethylamine;

and R₂ and R₃ are as defined for formula I.

1c)

R₁ is hydrogen, chlorine, bromine, methyl, methoxy, CF₃, NO₂,trifluoromethoxy, trifluorochloroethoxy, difluoromethoxy ordimethylamine;

and R₂ and R₃ are as defined for formula I.

1d)

R₁ is chlorine, methyl, methoxy, CF₃ or dimethylamine;

and R₂ and R₃ are as defined for formula I.

2a)

R₂ is phenoxy or phenylthio each of which is unsubstituted or mono-ordi-substituted by fluorine, chlorine, bromine, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₂ haloalkoxy having at least 2 fluorine atoms, nitro,cyano, allyl, propargyl,

2-phenylethynyl or by a further phenoxy radical that is unsubstituted orsubstituted by fluorine, chlorine, bromine or by methyl;

and R₁ and R₃ are as defined for formula I.

2b)

R₂ is phenoxy that is unsubstituted or substituted by fluorine,chlorine, bromine, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkoxy havingat least 2 fluorine atoms, cyano, nitro, allyl, propargyl,2-phenylethynyl or by a further phenoxy radical that is unsubstituted orsubstituted by fluorine, chlorine, bromine or by methyl;

and R₁ and R₃ are as defined for formula I.

2c)

R₂ is phenylthio that is unsubstituted or substituted by fluorine,chlorine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, C₁ -C₂ haloalkoxy having at least2 fluorine atoms, nitro, allyl, propargyl or by 2-phenylethynyl;

and R₁ and R₃ are as defined for formula I.

2d)

R₂ is phenoxy that is unsubstituted or substituted by chlorine, bromine,methyl, tert-butyl, methoxy, ethoxy, trifluoromethoxy, cyano, nitro,allyl, propargyl, 2-phenylethynyl or by a further phenoxy radical thatis unsubstituted or substituted by fluorine, bromine or by methyl;

and R₁ and R₃ are as defined for formula I.

3a)

R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by halogen; phenyl; phenylsubstituted by halogen, C₁ -C₄ alkyl and/or by nitro; benzyl; or benzylsubstituted by halogen, C₁ -C₄ alkyl and/or by nitro;

and R₁ and R₂ are as defined for formula I.

3b)

R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by fluorine or by chlorine;phenyl; phenyl substituted by chlorine, methyl or by nitro; benzyl; orbenzyl substituted by chlorine, methyl or by nitro;

and R₁ and R₂ are as defined for formula I.

4a)

R₁ is hydrogen, halogen, C₁ -C₄ alkyl, methoxy, ethoxy, CF₃, NO₂, C₁ -C₂haloalkoxy having at least 2 fluorine and/or 2 chlorine atoms,diethylamine or dimethylamine;

R₂ is phenoxy or phenylthio each of which is unsubstituted or mono-ordi-substituted by fluorine, chlorine, bromine, C₁ -C₄ alkyl, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkoxy having at least 2 fluorineatoms, cyano, nitro, allyl, propargyl, 2-phenylethynyl or by a furtherphenoxy radical that is unsubstituted or substituted by fluorine,chlorine, bromine or by methyl; and

R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by halogen; phenyl; phenylsubstituted by halogen, C₁ -C₄ alkyl and/or by nitro; benzyl; or benzylsubstituted by halogen, C₁ -C₄ alkyl and/or by nitro.

4b

R₁ is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy,CF₃, NO₂, C₁ -C₂ haloalkoxy having at least 2 fluorine atoms, ordimethylamine;

R₂ is phenoxy that is unsubstituted or substituted by fluorine,chlorine, bromine, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkoxy havingat least 2 fluorine atoms, cyano, nitro, allyl, propargyl,2-phenylethynyl or by a further phenoxy radical that is unsubstituted orsubstituted by fluorine, bromine or by methyl; and

R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by fluorine or by chlorine;phenyl; phenyl substituted by chlorine, methyl or by nitro; benzyl; orbenzyl substituted by chlorine, methyl or by nitro.

4c)

R₁ is hydrogen, chlorine, bromine, methyl, methoxy, CF₃, NO₂,trifluoromethoxy, trifluorochloroethoxy, difluoromethoxy ordimethylamine;

R₂ is phenylthio that is unsubstituted or substituted by fluorine,chlorine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, C₁ -C₂ haloalkoxy having at least2 fluorine atoms, nitro, allyl, propargyl or by 2-phenylethynyl; and

R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by fluorine or by chlorine;phenyl; phenyl substituted by chlorine, methyl or by nitro; benzyl; orbenzyl substituted by chlorine, methyl or by nitro.

4d)

R₁ is chlorine, methyl, methoxy, CF₃ or dimethylamine;

R₂ is phenoxy that is unsubstituted or substituted by chlorine, bromine,methyl, tert-butyl, methoxy, ethoxy, trifluoromethoxy, cyano, nitro,allyl, propargyl, 2-phenylethynyl or by a further phenoxy radical thatis unsubstituted or substituted by fluorine, bromine or by methyl; and

R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by fluorine or by chlorine;phenyl; phenyl substituted by chlorine, methyl or by nitro; benzyl; orbenzyl substituted by chlorine, methyl or by nitro.

Compounds of formula I preferred for their mode of action are asfollows:

1-N-methanesulfonyl-5-chloro-6-phenoxy-benzotriazole;

1-N-methanesulfonyl-5-chloro-6-(2-chlorophenoxy)-benzotriazole;

1-N-methanesulfonyl-5-chloro-6-(4-chlorophenoxy)-benzotriazole;

1-N-methanesulfonyl-5-chloro-6-(2,4-dibromophenoxy)-benzotriazole;

1-N-methanesulfonyl-5-chloro-6-(2-fluorophenoxy)-benzotriazole;

1-N-methanesulfonyl-5-chloro-6-(4-ethoxyphenoxy)-benzotriazole;

3-N-methanesulfonyl-5-chloro-6-phenoxy-benzotriazole;

3-N-methanesulfonyl-5-chloro-6-(2-chlorophenoxy)-benzotriazole;

3-N-methanesulfonyl-5-chloro-6-(4-chlorophenoxy)-benzotriazole;

3-N-methanesulfonyl-5-chloro-6-(2,4-dibromophenoxy)-benzotriazole;

3-N-methanesulfonyl-5-chloro-6-(2-fluorophenoxy)-benzotriazole; and

3-N-methanesulfonyl-5-chloro-6-(4-ethoxyphenoxy)-benzotriazole;

and mixtures of the 1-N- and 3-N-substituted structural isomers. Thecompounds of formula I are prepared

1) by reacting a compound of formula II ##STR3## with a compound offormula III

    Q--SO.sub.2 --R.sub.3                                      (III),

wherein R₁, R₂ and R₃ are as defined for formula I and M is hydrogen oran alkali metal, preferably sodium, potassium or lithium, and Q is ahalogen atom, preferably chlorine, or the radical O--SO₂ --R₃, in aninert solvent, in the presence or absence of a base, at temperaturesfrom -30° to 180° C., preferably from -10° to 80° C., under normal,reduced or elevated pressure, preferably normal pressure; or

2) by diazotizing a compound of formula IV ##STR4## wherein R₁, R₂ andR₃ are as defined for formula I, either

a) with an inorganic nitrite in a solvent, preferably in water or in amixture of water with an alcohol, preferably methanol or ethanol, or ina mixture of water with an ether, preferably dioxane or dimethoxyethane,in the presence of an acid, at temperatures from -30° to 180° C.,preferably from 0° to 80° C.; or

b) with an organic nitrite, preferably ethyl nitrite, amyl nitrite ortert-butyl nitrite, in a solvent, preferably an alcohol, such asmethanol or ethanol, or an ether, such as dioxane or dimethoxyethane, inthe presence or absence of an acid, at temperature from -30° to 180° C.,preferably from 0° to 80° C., under normal pressure or elevatedpressure.

Compounds of formula IIa ##STR5## wherein: R₁ is hydrogen, halogen, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy having at least twoidentical or different halogen atoms, CF₃, nitro or the group N(R')R",wherein R' and R" are each independently of the other C₁ -C₄ alkyl;

R₂ is phenoxy or phenylthio each of which is unsubstituted or mono-totri-substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy having at least two identical or different halogen atoms,cyano, nitro, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, phenyl, 2-phenylethynyl orby a further phenoxy radical that is unsubstituted or substituted byhalogen, C₁ -C₄ alkyl and/or by C₁ -C₄ alkoxy;

R₃ is alkyl, aryl or aralkyl having a maximum of 14 carbon atoms, theseradicals can be substituted by halogen, C₁ -C₄ alkyl and/or by nitro;

are novel with the exception of those compounds in which,simultaneously, R₁ is hydrogen and R₂ is5-(2-chloro4-trifluoromethylphenoxy) or R₁ is 6-chlorine and R₂ is5-phenoxy.

The compounds of formula IIa are prepared

3) by diazotizing a compound of formula V ##STR6## wherein R₁ and R₂ areas defined for formula IIa, either

3a) with an inorganic nitrite in a solvent, preferably in water or in amixture of water with an alcohol, preferably methanol or ethanol, or ina mixture of water with an ether, preferably dioxane or dimethoxyethane,in the presence of an acid, at temperatures from -30° to 180° C.,preferably from 0° to 80° C.; or

3b) with an organic nitrite, preferably ethyl nitrite, amyl nitrite ortert-butyl nitrite, in a solvent, preferably an alcohol, such asmethanol or ethanol, or an ether, such as dioxane or dimethoxyethane, inthe presence or absence of an acid, at temperatures from -30° to 180°C., preferably from 0° to 80° C., under normal pressure or elevatedpressure; or

4) by reacting a compound of formula VI ##STR7## wherein R₁ and R₂ areas defined for formula IIa and X is a halogen atom, preferably fluorineor chlorine, with hydrazine or hydrazine hydrate in a solvent,preferably an alcohol, such as methanol or ethanol, in the presence ofan acidbinding agent, preferably sodium carbonate, potassium carbonateor triethylamine, at the reflux temperature of the reaction medium, toform a compound of formula VII ##STR8## which is then reacted with achloroketone of formula VIII

    Cl--CH.sub.2 --CO--(C.sub.1 -C.sub.6 alkyl)                (VIII),

preferably chloroacetone, in an inert solvent in the presence of a base,at temperatures from 40° to 140° C., preferably from 60° to 120° C.

The following inert solvents are suitable for the processes describedabove: aliphatic, cycloaliphatic or aromatic hydrocarbons, for examplehexane, cyclohexane, toluene, xylene, petroleum ether or ligroin;chlorinated hydrocarbons, for example methylene chloride, chloroform,carbon tetrachloride, chlorobenzene; ethers, for example diethyl ether,diisopropyl ether, furan, tetrahydrofuran, dioxane; ketones, for exampleacetone, methyl ethyl ketone; alcohols, for example methanol, ethanol,isopropanol; esters, for example ethyl acetate, butyl acetate; nitriles,for example acetonitrile, propionitrile; acid amides, for exampledimethylformamide; sulfones and sulfoxide, for example dimethylsulfoxide, sulfolane.

Suitable bases or acid-binding agents are, for example, hydroxides,carbonates, hydrogen carbonates or alcoholates of alkali metals; andalso tertiary amines, for example, triethylamine, triisopropylamine,pyridine or 4-N,N-dimethylaminopyridine.

The above-described processes correspond to methods of synthesis thatare known from the literature. They are described, for example, in Chem.Reviews 46, 1 (1950) and in German Offenlegungsschrift 34 06 011. Thesynthesis of starting compounds of the type of formula IV is known fromU.S. Pat. No. 2,943,017.

Compounds with benzotriazolesulfonic acid structures are already known.Such compounds are described in DE-1 046 937, GB-885 843 and U.S. Pat.No. 2,943,017 as active ingredients that can be used as fungicides.

The known compounds, however, are not always able satisfactorily to meetthe requirements currently made of them as fungicides in practice, inparticular when used at low rates of application and against certainpests.

Surprisingly, it has been found that the compounds of formula I have,for practical field application purposes, a very advantageous biocidalspectrum for the control of phytopathogenic microorganisms, especiallyfungi. They have very advantageous curative, preventive and, inparticular, systemic properties and are used for protecting numerouscultivated plants.

The novel compounds of formula I have proved effective against specificgenera of the fungus class Fungi imperfecti (e.g. Cercospora),Basidiomycetes (e.g. Puccinia) and also Ascomycetes (e.g. Erysiphe andVenturia) and in particular against Oomycetes (e.g. Plasmopara andPhytophthora). In the field of plant protection they therefore representa valuable addition to compositions for controlling phytopathogenicfungi. For practical field application purposes they advantageouslyexhibit curative and preventive and also systemic properties and can beused for protecting numerous cultivated plants. With these compounds itis possible to inhibit or destroy the pests which occur on plants or onparts of plants (fruit, blossoms, leaves, stems, tubers, roots) indifferent crops of useful plants, while at the same time the parts ofplants which grow later are also protected, for example, againstphytopathogenic fungi. The compounds of formula I can also be used asdressing agents for protecting seeds (fruit, tubers, grains) and plantcuttings against fungus infections as well as against phytopathogenicfungi which occur in the soil.

The invention also relates to compositions comprising as activeingredient compounds of formula I, especially plant-protectingcompositions, and to their use in the agricultural sector or relatedfields.

The present invention further embraces the preparation of thosecompositions, which comprises homogeneously mixing the active ingredientwith one or more compounds or groups of compounds described herein. Theinvention furthermore relates to a method of treating plants, whichcomprises applying thereto the novel compounds of formula I or the novelcompositions.

Target crops to be protected within the scope of the present inventioncomprise e.g. the following species of plants: cereals (wheat, barley,rye, oats, rice, maize, sorghum and related crops); beet (sugar beet andfodder beet); pomes, drupes and soft fruit (apples, pears, plums,peaches, almonds, cherries, strawberries, raspberries and blackberries);leguminous plants (beans, lentils, peas, soybeans); oil plants (rape,mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoabeans, groundnuts); cucumber plants (cucumber, marrows, melons); fibreplants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons,grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocados, cinnamon, camphor) or plants such as tobacco, nuts, coffee,sugar cane, tea, peppers, vines, hops, bananas and natural rubberplants, as well as ornamentals.

The compounds of formula I are normally applied in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession, with further compounds. These furthercompounds can be fertilisers or micronutrient donors or otherpreparations that influence plant growth. They can also be selectiveherbicides, insecticides, fungicides, bactericides, nematicides,molluscicides or mixtures of several of these preparations, if desiredtogether with further carriers, surfactants or otherapplication-promoting adjuvants customarily employed in formulationtechnology.

Suitable carriers and adjuvants can be solid or liquid and correspond tothe substances ordinarily employed in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula I, or anagrochemical composition which comprises at least one of said compounds,is foliar application. The number of applications and the rate ofapplication depend on the risk of infestation by the correspondingpathogen. However, the compounds of formula I can also penetrate theplant through the roots via the soil (systematic action) if the locus ofthe plant is impregnated with a liquid formulation, or if the compoundsare applied in solid form to the soil, e.g. in granular form (soilapplication). In paddy rice crops, such granules may be applied inmetered amounts to the flooded rice field. The compounds of formula Imay, however, also be applied to seeds (coating) either by impregnatingthe seeds with a liquid formulation comprising a compound of formula I,or coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably,together with the adjuvants conventionally employed in formulationtechnology and are for this purpose advantageously formulated in knownmanner e.g. into emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions, dilute emulsions, wettable powders,soluble powders, dusts, granules and also encapsulations in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering, coatingor pouring, are chosen in accordance with the intended objectives andthe prevailing circumstances. Advantageous rates of application arenormally from 10 g to 5 kg of active ingredient (a.i.) per ha,preferably from 20 g to 1 kg a.i./ha.

The formulations, i.e. the compositions, preparations or mixturescomprising the compound (active ingredient) of formula I and, whereappropriate, a solid or liquid adjuvant, are prepared in known manner,e.g. by homogeneously mixing and/or grinding the active ingredients withextenders, e.g. solvents, solid carriers and, where appropriate,surfaceactive compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycol,ethylene glycol monomethyl or monoethyl ether, ketones such ascyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethylformamide, as well as vegetable oils orepoxidised vegetable oils, such as epoxidised coconut oil or soybeanoil; or water.

The solid carriers use e.g. for dusts and dispersible powders arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable non-sorbent carriers are, for example,calcite or sand. In addition, a great number of pregranulated materialsof inorganic nature can be used, e.g. especially dolomite or pulverisedplant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Both so-called water-soluble soaps and water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyllaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially alkanesulfonates, fatty alcohol sulfates, sulfonatedbenzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are usually in the form ofalkali metal salts, alkaline earth metal salts or unsubstituted orsubstituted ammonium salts and contain a C₈ -C₂₂ alkyl radical, whichalso includes the alkyl moiety of acyl radicals, e.g. the sodium orcalcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixtureof fatty alcohol sulfates obtained from natural fatty acids. Thesecompounds also comprise the salts of sulfated and sulfonated fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a condensate ofnaphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoricacid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethyleneoxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethyleneethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methyl sulfates or ethyl sulfates, e.g.stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ammoniumbromide.

Further surfactants customarily employed in formulation technology areknown to the person skilled in the art or can be taken from the relevantspecialist literature.

The agrochemical compositions usually comprise 0.1 to 99% by weight,preferably 0.1 to 95% by weight, of a compound of formula I, 99.9 to 1%by weight, preferably 99.9 to 5% by weight, of a solid or liquidadjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of asurfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further auxiliaries such asstabilisers, antifoams, viscosity regulators, binders, tackifiers aswell as fertilisers or other active ingredients for obtaining specialeffects.

The following Examples serve to illustrate the invention in greaterdetail, without limiting it.

1. PREPARATION EXAMPLES 1.1 Preparation of5-(2,3-dichlorophenoxy)-4-chloro-2nitroaniline ##STR9##

A mixture of 171 g of 2,3-dichlorophenol and 186 g of4,5-dichloro-2-nitroaniline is heated to 150° C. 101 g of a 50%potassium hydroxide solution are added dropwise to the dark-red liquidover a period of 1 hour. The water of reaction formed is distilled offwith a small amount of phenol. The reaction mixture is stirred overnightat 150° C. and then, at that temperature, 450 ml of dimethylformamideare added. The solution is allowed to cool and is all poured onto amixture of 3 1 of water and 150 ml of concentrated sodium hydroxidesolution. The greenish suspension is stirred at room temperature for 1hour, and the crystals that form are filtered off and washed neutralwith water and then dried. The still moist yellowish crystals are usedin crude form in the next reaction step.

1.2 Preparation of 4-chloro-5-(2,3-dichlorophenoxy)-ophenylenediamine##STR10##

17 ml of glacial acetic acid are added dropwise over a period of 80minutes to a suspension of 80 g of iron powder in 400 ml of water andthe mixture is then heated to reflux temperature. After the addition of100 ml of chlorobenzene, the nitroaniline prepared in Example 1.1 isadded to the reaction mixture over a period of 2 hours. During thecourse of this addition an exothermic reaction is observed. Afterheating at reflux for 14 hours the reduction of the nitro group iscomplete. The mixture is allowed to cool, diluted with 500 ml ofchlorobenzene and the aqueous phase is rendered alkaline with sodiumcarbonate solution. The organic phase is removed, dried with sodiumsulfate and concentrated under reduced pressure. After the addition of100 ml of petroleum ether to the crude product, a crystalline mass isobtained which is filtered off and washed with petroleum ether, yieldingthe title compound having a melting point of 110°-112° C.

1.3 Preparation of 5-chloro- 6-(2,3-dichlorophenoxy)benzotriazole##STR11##

7.5 g of diamine prepared in Example 1.2 are suspended in 50 ml of waterand, at room temperature, 2.9 ml of acetic acid are added. After heatingbriefly to 60° C., the reaction solution is cooled to 5° C. and, at thattemperature, a solution of 3.9 g of sodium nitrite in 12 ml of water isadded. The mixture is then heated at 80° C. for 3 hours, and the brownsuspension is cooled and filtered. The crystals obtained arerecrystallised twice from ethanol/water, yielding the title compoundhaving a metling point of 173° C.

1.4 Preparation of the isomeric mixture of 1-N-(methanesulfonyl)- and3-N-(methanesulfonyl)-5-chloro-6-(2,3dichlorophenoxy)-benzotriazole##STR12##

3.1 g of benzotriazole from Example 1.3 are dissolved in 30 ml ofdimethylformamide and 2.78 ml of triethylamine. 1.56 ml ofmethanesulfonyl chloride are added dropwise to the brown solutionwithout external heating, in the course of which the temperature risesto 45° C. The mixture is then stirred at room temperature for one hourand the suspension is poured into 500 ml of water. The white productthat precipitates is filtered off and recrystallised from ethanol,yielding the desired product in the form of an isomeric mixture having amelting point of 178°-180° C.

                                      TABLE 1                                     __________________________________________________________________________     ##STR13##                                                                    Comp.                                                                         No. R.sub.1 R.sub.2       R.sub.3                                                                             Physical data                                 __________________________________________________________________________    1.1 Cl      OPh           CH(CH.sub.3).sub.2                                  1.2 CH.sub.3                                                                              OPh           C.sub.2 H.sub.5                                     1.3 Cl      OPh           CH.sub.3                                                                            m.p. 100-104° C.                       1.4 CH.sub.3                                                                              OPh           CH.sub.3                                            1.5 CH.sub.3                                                                              OPh           CH(CH.sub.3).sub.2                                  1.6 Cl      OPh-2-Cl      CH.sub.3                                                                            m.p. 152-154° C.                       1.7 Cl      OPh-2-Cl      C.sub.2 H.sub.5                                     1.8 Cl      OPh-2-Cl      C.sub.6 H.sub.5                                     1.9 Cl      OPh-3-Cl      CH.sub.3                                                                            m.p. 76-79° C.                         1.10                                                                              Cl      OPh-4-Cl      C.sub.3 H.sub.7 (n)                                 1.11                                                                              Cl      OPh-4-Cl      CH.sub.2Ph                                          1.12                                                                              Cl      OPh-4-Cl      C.sub.6 H.sub.5                                     1.13                                                                              Cl      OPh-4-Cl      CH.sub.3                                                                            m.p. 144-145° C.                       1.14                                                                              Cl      OPh-2-F       CH.sub.3                                                                            m.p. 132-133° C.                       1.15                                                                              Cl      OPh-2-Br      C.sub.4 H.sub.9                                     1.16                                                                              Cl      OPh-2,4-(Br).sub.2                                                                          CH.sub.3                                                                            m.p. 147-148° C.                       1.17                                                                              CH.sub.3                                                                              OPh-4-Cl      CH.sub.3                                            1.18                                                                              OCF.sub.3                                                                             OPh-2-Cl      CH.sub.3                                            1.19                                                                              NO.sub.2                                                                              OPh           C.sub.6 H.sub.5                                     1.20                                                                              NO.sub.2                                                                              OPh-4-Cl      CH.sub.3                                            1.21                                                                              C.sub.4 H.sub.9                                                                       OPh-4-C(CH.sub.3).sub.3                                                                     C.sub.3 H.sub.7 (n)                                 1.22                                                                              C.sub.4 H.sub.9                                                                       SPh           CH.sub.3                                            1.23                                                                              N(CH.sub.3).sub.2                                                                     OPh-4-Cl      CH.sub.3                                            1.24                                                                              N(CH.sub.3).sub.2                                                                     OPh-2-F       CH.sub.3                                            1.25                                                                              N(CH.sub.3).sub.2                                                                     SPh-4-Cl      CH.sub.3                                            1.26                                                                              CN      OPh-4-Cl      CH.sub.3                                            1.27                                                                              OCF.sub.2 CFHCF.sub.3                                                                 OPh-4-Cl      CH.sub.3                                            1.28                                                                              OCF.sub.2 CFClH                                                                       SPh-4-Cl      CH.sub.3                                            1.29                                                                              OCF.sub.2 CFClH                                                                       SPh-4-Cl      CH(CH.sub.3).sub.2                                  1.30                                                                              Cl      OPh-4-OC.sub.2 H.sub.5                                                                      CH.sub.3                                                                            m.p. 164-166° C.                       1.31                                                                              Cl      OPh-4-OPh     CH.sub.3                                                                            m.p. 161-163° C.                       1.32                                                                              Cl      OPh-4-(OPh-4-F)                                                                             CH.sub.3                                            1.33                                                                              Cl      OPh-4Ph       CH.sub.3                                                                            m.p. 200-205° C.                       1.34                                                                              Cl      OPh-4Ph       CH(CH.sub.3).sub.3                                  1.35                                                                              Cl      OPh-4-(OPh-4-CH.sub.3)                                                                      CH.sub.3                                            1.36                                                                              Cl      OPh-4-(CCPh)  CH.sub.3                                            1.37                                                                              Cl      OPh-4-Allyl   CH.sub.3                                            1.38                                                                              Cl      OPh-3,5-(Cl).sub.2                                                                          CH.sub.3                                                                            m.p. 143-145° C.                       1.39                                                                              Cl      OPh-2,3-(CH.sub.3).sub.2                                                                    CH.sub.3                                                                            m.p. 140-144° C.                       1.40                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          CH(CH.sub.3).sub.2                                                                  m.p. 95-98° C.                         1.41                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          C.sub.3 H.sub.7 (n)                                                                 m.p. 94-96° C.                         1.42                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          C.sub.6 H.sub.5                                                                     m.p. 115-118° C.                       1.43                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          Ph-4-CH.sub.3                                                                       m.p. 134-137° C.                       1.44                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          Ph-4-NO.sub.2                                                                       m.p. 172-175° C.                       1.45                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          Ph-4-Cl                                                                             m.p. 130-132° C.                       1.46                                                                              Cl      SPh-4-Cl      CH.sub.3                                                                            m.p. 135-138° C.                       1.47                                                                              Cl      SPh-4-CH.sub.3                                                                              CH.sub.3                                            1.48                                                                              Cl      OPh-2,4-(F).sub.2                                                                           CH.sub.3                                            1.49                                                                              Cl      OPh-2-Cl-4-F  CH.sub.3                                                                            m.p. 191-193° C.                       1.50                                                                              Cl      OPh-3-NO.sub.2                                                                              CH.sub.3                                            1.51                                                                              Cl      OPh-2-NO.sub.2 -4-Cl                                                                        CH.sub.3                                            1.52                                                                              Cl      OPh-4-OCF.sub.3                                                                             CH.sub.3                                            1.53                                                                              CH.sub.3                                                                              OPh-3-OC.sub.2 H.sub.5                                                                      CH.sub.3                                            1.54                                                                              CH.sub.3                                                                              OPh-4-CN      CH.sub.3                                            1.55                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          CH.sub.2Ph                                          1.56                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          CH.sub.2 CF.sub.3                                   1.57                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          CH.sub.3                                                                            m.p. 178-180° C.                       1.58                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          C.sub.2 H.sub.5                                     1.59                                                                              Cl      OPh-4-F       CH.sub.3                                                                            m.p. 114-116° C.                       1.60                                                                              Cl      OPh-4-CH.sub.3                                                                              CH.sub.3                                                                            m.p. 165° C.                           1.61                                                                              Cl      OPh-3,4-(CH.sub.3).sub.2                                                                    CH.sub.3                                                                            m.p. 152° C.                           1.62                                                                              Cl      OPh-3-CF.sub.3                                                                              CH.sub.3                                                                            m.p. 109° C.                           1.63                                                                              Cl      OPh-3,5-(CH.sub.3).sub.2                                                                    CH.sub.3                                                                            m.p. 150° C.                           1.64                                                                              Cl      SPh           CH.sub.3                                                                            m.p. 138-140° C.                       1.65                                                                              Cl      SPh-4-C(CH.sub.3).sub.3                                                                     CH.sub.3                                                                            m.p. 128° C.                           1.66                                                                              Cl      OPh-4-C.sub.2 H.sub.5                                                                       CH.sub.3                                                                            m.p. 153° C.                           1.67                                                                              Cl      OPh-2,4-(Cl).sub.2                                                                          CH.sub.3                                                                            m.p. 187-189° C.                       1.68                                                                              Cl      SPh-2,5-(Cl).sub.2                                                                          CH.sub.3                                                                            m.p. 200-204° C.                       1.69                                                                              Cl      OPh-3-OCF.sub.3                                                                             CH.sub.3                                                                            m.p. 149-151° C.                       1.70                                                                              Cl      OPh-3,4-(CH.sub.3).sub.2                                                                    CF.sub.3                                                                            m.p. 95° C.                            1.71                                                                              Cl      SPh-4-F       CH.sub.3                                                                            m.p. 140-151° C.                       1.72                                                                              Cl      OPh-4-CN      CH.sub.3                                                                            m.p. 158-160° C.                       1.73                                                                              Cl      OPh-2,4-(CH.sub.3).sub.2                                                                    CH.sub.3                                                                            m.p. 188-190° C.                       1.74                                                                              Cl      OPh-4-Cl      CF.sub.3                                                                            m.p. 76-78° C.                         1.75                                                                              Cl      OPh-3,5-(CH.sub.3).sub.2                                                                    CF.sub.3                                                                            m.p. 112° C.                           1.76                                                                              Cl      OPh-4-CH.sub.3                                                                              CF.sub.3                                                                            m.p. 122° C.                           1.77                                                                              Cl      OPh-2,4-(Cl).sub.2                                                                          CF.sub.3                                                                            oil                                           1.78                                                                              Cl      SPh-4-C(CH.sub.3).sub.3                                                                     CF.sub.3                                                                            m.p. 119° C.                           1.79                                                                              Cl      SPh-4-C(CH.sub.3).sub.3                                                                     Ph    m.p. 131° C.                           1.80                                                                              Cl      OPh-2-F       CF.sub.3                                                                            m.p. 113° C.                           1.81                                                                              Cl      OPh-2,3-(Cl).sub.2                                                                          CF.sub.3                                                                            m.p. 107° C.                           1.82                                                                              Cl      OPh-3-OPh     CH.sub.3                                                                            m.p. 109-115° C.                       1.83                                                                              H       OPh-4-OC.sub.2 H.sub.5                                                                      CH.sub.3                                                                            m.p. 50-65° C.                         1.84                                                                              H       OPh-2-Cl,4-CF.sub.3                                                                         CH.sub.3                                                                            m.p. 85-96° C.                         1.85                                                                              Cl      OPh-3,4(OCH.sub.2 O)                                                                        CH.sub.3                                                                            m.p. 145-149° C.                       1.86                                                                              Cl      O Ph-2-OC.sub.2 H.sub.5                                                                     CH.sub.3                                                                            m.p. 147-149° C.                       1.87                                                                              Cl      OPh-4-OCH.sub.3                                                                             CH.sub.3                                                                            m.p. 151-153° C.                       1.88                                                                              Cl      OPh-2-OCH.sub.3                                                                             CH.sub.3                                                                            m.p. 160-165° C.                       1.89                                                                              Cl      OPh-4-OC.sub.3 H.sub.7 (n)                                                                  CH.sub.3                                                                            m.p. 176-179° C.                       1.90                                                                              Cl      OPh-3-OCH.sub.3                                                                             CH.sub.3                                                                            m.p. 130-131° C.                       1.91                                                                              Cl      OPh-3,5-(OCH.sub.3).sub.2                                                                   CH.sub.3                                                                            m.p. 136-139° C.                       1.92                                                                              Cl      SPh-4-OCH.sub.3                                                                             CH.sub.3                                                                            m.p. 134-138° C.                       1.93                                                                              Cl      OPh           CF.sub.3                                            1.94                                                                              Cl      OPh           Ph                                                  1.95                                                                              Cl      OPh-2-Cl      CF.sub.3                                            1.96                                                                              Cl      OPH-2-F       CF.sub.3                                            1.97                                                                              Cl      OPh-2-F       Ph                                                  1.98                                                                              Cl      OPh-4-Cl      CF.sub.3                                            1.99                                                                              Cl      OPh-4-F       CF.sub.3                                            1.100                                                                             Cl      OPh-4-CN      CF.sub.3                                            1.101                                                                             Cl      OPh-4-OPh     CF.sub.3                                            1.102                                                                             Cl      OPh-4-OPh     Ph                                                  1.103                                                                             Cl      OPh-4-Ph      CF.sub.3                                            1.104                                                                             Cl      OPh-4-C(CH.sub.3).sub.3                                                                     CH.sub.3                                            1.105                                                                             Cl      OPh-4-C(CH.sub.3).sub.3                                                                     CF.sub.3                                            1.106                                                                             Cl      OPh-4-C(CH.sub.3).sub.3                                                                     Ph                                                  1.107                                                                             Cl      OPh-4-OCF.sub.3                                                                             CF.sub.3                                            1.108                                                                             Cl      SPh           CF.sub.3                                            1.109                                                                             Cl      S Ph-4-F      CF.sub.3                                            1.110                                                                             Cl      OPh-3-OPh     CF.sub.3                                            1.111                                                                             Cl      OPh-2,4-(CH.sub.3).sub.2                                                                    CF.sub.3                                            1.112                                                                             Cl      OPh-2-(n)C.sub.3 H.sub.7                                                                    CH.sub.3                                            1.113                                                                             Cl      OPh-4-(n)C.sub.3 H.sub.7                                                                    CH.sub.3                                            1.114                                                                             Cl      OPh-4-CH(CH.sub.3).sub.3                                                                    CH.sub.3                                            1.115                                                                             Cl      OPh-2-CH(CH.sub.3).sub.2                                                                    CH.sub.3                                            1.116                                                                             Cl      OPh-3-CH(CH.sub.3).sub.2                                                                    CH.sub.3                                            1.117                                                                             Cl      OPh-2-CH(CH.sub.3)CH.sub.2 CH.sub.3                                                         CH.sub.3                                            1.118                                                                             Cl      OPh-4-CH(CH.sub.3)CH.sub.2 CH.sub.3                                                         CH.sub.3                                            1.119                                                                             Cl      OPh-2-C(CH.sub.3).sub.3                                                                     CH.sub.3                                            1.120                                                                             Cl      OPh-3-C(CH.sub.3).sub.3                                                                     CH.sub.3                                            1.121                                                                             Cl      OPh-2-SCH.sub.3                                                                             CH.sub.3                                            1.122                                                                             Cl      OPh-2-SC.sub.2 H.sub.5                                                                      CH.sub.3                                            1.123                                                                             Cl      OPh-2-OCH(CH.sub.3).sub.2                                                                   CH.sub.3                                            1.124                                                                             Cl      OPh-4-OC.sub.4 H.sub.9 (n)                                                                  CH.sub.3                                            1.125                                                                             Cl      OPh-3-N(C.sub.2 H.sub.5).sub.2                                                              CH.sub.3                                            1.126                                                                             Cl      OPh-2,3-(OCH.sub.3).sub.2                                                                   CH.sub.3                                                                            m.p- 142-143° C.                       1.127                                                                             Cl      OPh-3-N(CH.sub.3).sub.2                                                                     CH.sub.3                                            1.128                                                                             Cl      OPh-4-SCH.sub.3                                                                             CH.sub.3                                                                            m.p. 148-150° C.                       1.129                                                                             Cl      OPh-3,4,5-(OCH.sub.3).sub.3                                                                 CH.sub.3                                            1.130                                                                             Cl      OPh-3-CH.sub.3 -4-SCH.sub.3                                                                 CH.sub.3                                                                            m.p. 103-107° C.                       1.131*                                                                            5-Cl    6-(OPh-4-OC.sub.2 H.sub.5)                                                                  CH.sub.3                                                                            m.p. 186° C.                           1.132*                                                                            6-Cl    5-(OPh-4-OC.sub.2 H.sub.5)                                                                  CH.sub.3                                                                            m.p. 161° C.                           __________________________________________________________________________     *Isomeric mixtures with respect to R.sub.1 and R.sub.2 in position 5 or 6     *Individual isomers                                                      

                  TABLE 2                                                         ______________________________________                                         ##STR14##                                                                    Comp.                                 Physical                                No.   R.sub.1  R.sub.2        R.sub.3 data                                    ______________________________________                                        2.1   Cl       OPh            CH.sub.3                                        2.2   Cl       OPh-3-Cl       CH.sub.3                                        2.3   Cl       OPh-4-Cl       CH.sub.3                                        2.4   Cl       OPh-4-Cl       CH(CH.sub.3).sub.2                              2.5   CH.sub.3 OPh-4-Cl       CH.sub.3                                        2.6   CH.sub.3 OPh-2-F        CH.sub.3                                        2.7   CH.sub.3 OPh-2,3-(Cl).sub.2                                                                           CH.sub.3                                        2.8   CH.sub.3 OPh-4-Cl       CH.sub.2Ph                                      2.9   Cl       OPh-2-F        CH.sub.3                                        2.10  Cl       OPh-2-Cl       CH.sub.3                                        2.11  Cl       OPh-4-Cl       Ph                                              2.12  Cl       OPh-4-Cl       CH.sub.2Ph                                      2.13  Br       OPh-4-Cl       CH.sub.3                                        2.14  NO.sub.2 OPh-4-Cl       CH.sub.3                                        2.15  CF.sub.3 OPh-2-Cl       CH.sub.3                                        2.16  OCHF.sub.2                                                                             OPh-4-Cl       CH.sub.3                                        2.17  Cl       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        2.18  Cl       OPh-4-Ph       CH.sub.3                                        2.19  Br       OPh-4-Ph       CH.sub.3                                        2.20  Br       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        2.21  Br       OPh-3-OPh      CH.sub.3                                        2.22  Cl       OPh-4-Cl       Ph-4-CH.sub.3                                   2.23  Cl       OPh-4-OC.sub.2 H.sub.5                                                                       CH.sub.3                                        2.24  Cl       OPh-4-OCH.sub.3                                                                              CH.sub.3                                        2.25  Cl       OPh-3,5-(OCH.sub.3).sub.2                                                                    CH.sub.3                                        2.26  CH.sub.3 OPh-4-OPh      CH.sub.3                                        2.27  F        OPh-2-F        CH.sub.3                                        2.28  H        OPh-4-Cl       CH.sub.3                                        2.29  H        SPh-2-Cl       CH.sub.3                                        2.30  H        OPh-4-OCH.sub.3                                                                              CH.sub.3                                        2.31  H        OPh-4-OPh      CH.sub.3                                        2.32  H        OPh-2-Cl-4-F   CH.sub.3                                        2.33  H        OPh-3-Cl       C.sub.6 H.sub.5                                 2.34  H        OPh            CH(CH.sub.3).sub.3                              2.35  H        SPh            CH.sub.3                                        2.36  H        OPh-4-OPh      CH.sub.3                                        2.37  H        OPh-2,3-(Cl).sub.2                                                                           CH.sub.3                                        2.38  Cl       OPh-4-CH.sub.3 CH.sub.3                                        2.39  Cl       OPh-4-NO.sub.2 CH.sub.3                                        2.40  Cl       SPh-4-Cl       CH.sub.3                                        2.41  Cl       SPh-4-OCH.sub.3                                                                              CH.sub.3                                        2.42  Cl       SPh            CH.sub.3                                        2.43  Cl       OPh-2,4-Cl.sub.2                                                                             CH.sub.3                                        2.44  Cl       OPh-2,3-Cl.sub.2                                                                             CH.sub.3                                        2.45  Cl       OPh-2,3-(CH.sub.3).sub.2                                                                     CH.sub.3                                        2.46  Cl       OPh-4-F        CH.sub.3                                        2.47  Cl       OPh-4-CH.sub.3 CH.sub.3                                        2.48  Cl       OPh-2-Cl,4-F   CH.sub.3                                        2.49  Cl       OPh-2,4-(CH.sub.3).sub.2                                                                     CH.sub.3                                        2.50  Cl       SPh-4-F        CH.sub.3                                        ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                         ##STR15##                                                                    Comp.                                 Physical                                No.   R.sub.1  R.sub.2        R.sub.3 data                                    ______________________________________                                        3.1   Cl       OPh            CH.sub.3                                        3.2   Cl       OPh-3-Cl       CH.sub.3                                        3.3   Cl       OPh-4-Cl       CH.sub.3                                        3.4   Cl       OPh-4-Cl       CH(CH.sub.3).sub.2                              3.5   CH.sub.3 OPh-4-Cl       CH.sub.3                                        3.6   CH.sub.3 OPh-2-F        CH.sub.3                                        3.7   CH.sub.3 OPh-2,3-(Cl).sub.2                                                                           CH.sub.3                                        3.8   CH.sub.3 OPh-4-Cl       CH.sub.2Ph                                      3.9   Cl       OPh-2-F        CH.sub.3                                        3.10  Cl       OPh-2-Cl       CH.sub.3                                        3.11  Cl       OPh-4-Cl       Ph                                              3.12  Cl       OPh-4-Cl       CH.sub.2Ph                                      3.13  Br       OPh-4-Cl       CH.sub.3                                        3.14  NO.sub.2 OPh-4-Cl       CH.sub.3                                        3.15  CF.sub.3 OPh-2-Cl       CH.sub.3                                        3.16  OCHF.sub.2                                                                             OPh-4-Cl       CH.sub.3                                        3.17  Cl       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        3.18  Cl       OPh-4-Ph       CH.sub.3                                        3.19  Br       OPh-4-Ph       CH.sub.3                                        3.20  Br       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        3.21  Br       OPh-3-OPh      CH.sub.3                                        3.22  Cl       OPh-4-Cl       Ph-4-CH.sub.3                                   3.23  Cl       OPh-4-OC.sub.2 H.sub.5                                                                       CH.sub.3                                        3.24  Cl       OPh-4-OCH.sub.3                                                                              CH.sub.3                                        3.25  Cl       OPh-3,5-(OCH.sub.3).sub.2                                                                    CH.sub.3                                        3.26  CH.sub.3 OPh-4-OPh      CH.sub.3                                        3.27  F        OPh-2-F        CH.sub.3                                        3.28  H        OPh-4-Cl       CH.sub.3                                        3.29  H        SPh-2-Cl       CH.sub.3                                        3.30  H        OPh-4-OCH.sub.3                                                                              CH.sub.3                                        3.31  H        OPh-4-OPh      CH.sub.3                                        3.32  H        OPh-2-Cl-4-F   CH.sub.3                                        3.33  H        OPh-3-Cl       C.sub.6 H.sub.5                                 3.34  H        OPh            CH(CH.sub.3).sub.3                              3.35  H        SPh            CH.sub.3                                        3.36  H        OPh-4-Ph       CH.sub.3                                        3.37  H        OPh-2,3-(Cl).sub.2                                                                           CH.sub.3                                        3.38  Cl       OPh-4-CH.sub.3 CH.sub.3                                        3.39  Cl       OPh-4-NO.sub.2 CH.sub.3                                        3.40  Cl       SPh-4-Cl       CH.sub.3                                        3.41  Cl       SPh-4-OCH.sub.3                                                                              CH.sub.3                                        3.42  Cl       SPh            CH.sub.3                                        3.43  Cl       OPh-2,4-Cl.sub.2                                                                             CH.sub.3                                        3.44  Cl       OPh-2,3-Cl.sub.2                                                                             CH.sub.3                                        3.45  Cl       OPh-2,3-(CH.sub.3).sub.2                                                                     CH.sub.3                                        3.46  Cl       OPh-4-F        CH.sub.3                                        3.47  Cl       OPh-4-CH.sub.3 CH.sub.3                                        3.48  Cl       OPh-2-Cl,4-F   CH.sub.3                                        3.49  Cl       OPh-2,4-(CH.sub.3).sub.2                                                                     CH.sub.3                                        3.50  Cl       SPh-4-F        CH.sub.3                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                         ##STR16##                                                                    Comp.                                 Physical                                No.   R.sub.1  R.sub.2        R.sub.3 data                                    ______________________________________                                        4.1   Cl       OPh            CH.sub.3                                        4.2   Cl       OPh-3-Cl       CH.sub.3                                        4.3   Cl       OPh-4-Cl       CH.sub.3                                                                              m.p.                                                                          140-                                                                          142° C.                          4.4   Cl       OPh-4-Cl       CH(CH.sub.3).sub.2                              4.5   CH.sub.3 OPh-4-Cl       CH.sub.3                                        4.6   CH.sub.3 OPh-2-F        CH.sub.3                                        4.7   CH.sub.3 OPh-2,3-(Cl).sub.2                                                                           CH.sub.3                                        4.8   CH.sub.3 OPh-4-Cl       CH.sub.2Ph                                      4.9   Cl       OPh-2-F        CH.sub.3                                        4.10  Cl       OPh-2-Cl       CH.sub.3                                        4.11  Cl       OPh-4-Cl       Ph                                              4.12  Cl       OPh-4-Cl       CH.sub.2Ph                                      4.13  Br       OPh-4-Cl       CH.sub.3                                        4.14  NO.sub.2 OPh-4-Cl       CH.sub.3                                        4.15  CF.sub.3 OPh-2-Cl       CH.sub.3                                        4.16  OCHF.sub.2                                                                             OPh-4-Cl       CH.sub.3                                        4.17  Cl       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        4.18  Cl       OPh-4-Ph       CH.sub.3                                        4.19  Br       OPh-4-Ph       CH.sub.3                                        4.20  Br       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        4.21  Br       OPh-3-OPh      CH.sub.3                                        4.22  Cl       OPh-4-Cl       Ph-4-CH.sub.3                                   4.23  Cl       OPh-4-OC.sub.2 H.sub.5                                                                       CH.sub.3                                        4.24  Cl       OPh-4-OCH.sub.3                                                                              CH.sub.3                                                                              m.p.                                                                          130° C.                          4.25  Cl       OPh-3,5-(OCH.sub.3).sub.2                                                                    CH.sub.3                                        4.26  CH.sub.3 OPh-4-(OPh)    CH.sub.3                                        4.27  F        OPh-2-F        CH.sub.3                                        4.28  H        OPh-4-Cl       CH.sub.3                                        4.29  H        SPh-2-F        CH.sub.3                                        4.30  H        OPh-4-OCH.sub.3                                                                              CH.sub.3                                        4.31  H        OPh-4-OPh      CH.sub.3                                        4.32  H        OPh-2-Cl-4-F   CH.sub.3                                        4.33  H        OPh-3-Cl       C.sub.6 H.sub.5                                 4.34  H        OPh            CH(CH.sub.3).sub.3                              4.35  H        SPh            CH.sub.3                                        4.36  H        OPh-4-OPh      CH.sub.3                                        4.37  H        OPh-2,3-(Cl.sub.2).sub.2                                                                     CH.sub.3                                        4.38  H        OPh-4-OC.sub.2 H.sub.5                                                                       CH.sub.3                                                                              m.p.                                                                          133-                                                                          135° C.                          4.39  Cl       OPh-4-CH.sub.3 CH.sub. 3                                       4.40  Cl       SPh-4-NO.sub.2 CH.sub.3                                        4.41  Cl       SPh-4-Cl       CH.sub.3                                        4.42  Cl       SPh-4-OCH.sub.3                                                                              CH.sub.3                                        4.43  Cl       SPh            CH.sub.3                                        4.44  Cl       OPh-2,4-Cl.sub.2                                                                             CH.sub.3                                        4.45  Cl       OPh-2,3-Cl.sub.2                                                                             CH.sub.3                                        4.46  Cl       OPh-2,3-(CH.sub.3).sub.2                                                                     CH.sub.3                                        4.47  Cl       OPh-4-F        CH.sub.3                                        4.48  Cl       OPh-4-CH.sub.3 CH.sub.3                                        4.49  Cl       OPh-2-Cl,4-F   CH.sub.3                                        4.50  Cl       OPh-2,4-(CH.sub.3).sub.2                                                                     CH.sub.3                                        4.51  Cl       SPh-4-F        CH.sub.3                                        ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR17##                                                                    Comp.                                 Physical                                No.   R.sub.1  R.sub.2        R.sub.3 data                                    ______________________________________                                        5.1   Cl       OPh            CH.sub.3                                        5.2   Cl       OPh-3-Cl       CH.sub.3                                        5.3   Cl       OPh-4-Cl       CH.sub.3                                        5.4   Cl       OPh-4-Cl       CH(CH.sub.3).sub.2                              5.5   CH.sub.3 OPh-4-Cl       CH.sub.3                                        5.6   CH.sub.3 OPh-2-F        CH.sub.3                                        5.7   CH.sub.3 OPh-2,3-(Cl).sub.2                                                                           CH.sub.3                                        5.8   CH.sub.3 OPh-4-Cl       CH.sub.2Ph                                      5.9   Cl       OPh-2-F        CH.sub.3                                        5.10  Cl       OPh-2-Cl       CH.sub.3                                        5.11  Cl       OPh-4-Cl       Ph                                              5.12  Cl       OPh-4-Cl       CH.sub.2Ph                                      5.13  Br       OPh-4-Cl       CH.sub.3                                        5.14  NO.sub.2 OPh-4-Cl       CH.sub.3                                        5.15  CF.sub.3 OPh-2-Cl       CH.sub.3                                        5.16  OCHF.sub.2                                                                             OPh-4-Cl       CH.sub.3                                        5.17  Cl       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        5.18  Cl       OPh-4-Ph       CH.sub.3                                        5.19  Br       OPh-4-Ph       CH.sub.3                                        5.20  Br       OPh-4-(OPh-4-F)                                                                              CH.sub.3                                        5.21  Br       OPh-3-OPh      CH.sub.3                                        5.22  Cl       OPh-4-Cl       Ph-4-CH.sub.3                                   5.23  Cl       OPh-4-OC.sub.2 H.sub.5                                                                       CH.sub.3                                        5.24  Cl       OPh-4-OCH.sub.3                                                                              CH.sub.3                                        5.25  Cl       OPh-3,5-(OCH.sub.3).sub.2                                                                    CH.sub.3                                        5.26  CH.sub.3 OPh-4-OPh      CH.sub.3                                        5.27  F        OPh-2-F        CH.sub.3                                        ______________________________________                                    

Formulation Examples for active ingredients of formula I (throughout,percentages are by weight)

    ______________________________________                                        2.1. Wettable powders                                                                             a)       b)      c)                                       ______________________________________                                        a compound of the Tables                                                                          25%      50%     75%                                      sodium lignosulfonate                                                                             5%        5%     --                                       sodium laurylsulfate                                                                              3%       --       5%                                      sodium diisobutylnaphthalenesulfonate                                                             --        6%     10%                                      octylphenol polyethylene glycol ether                                                             --        2%     --                                       (7-8 mol of ethylene oxide)                                                   highly dispersed silicic acid                                                                     5%       10%     10%                                      kaolin              62%      27%     --                                       ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        2.2. Emulsifiable concentrate                                                 a compound of the Tables                                                                             10%                                                    octylphenol polyethylene glycol ether                                                                 3%                                                    (4-5 mol of ethylene oxide)                                                   calcium dodecylbenzenesulfonate                                                                       3%                                                    castor oil polyglycol ether                                                                           4%                                                    (35 mol of ethylene oxide)                                                    cyclohexanone          34%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of any desired concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        2.3. Dusts           a)     b)                                                ______________________________________                                        a compound of the Tables                                                                            5%     8%                                               talcum               95%    --                                                kaolin               --     92%                                               ______________________________________                                    

Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill.

    ______________________________________                                        2.4. Extruder granules                                                        a compound of the Tables                                                                          10%                                                       sodium lignosulfonate                                                                              2%                                                       carboxymethylcellulose                                                                             1%                                                       kaolin              87%                                                       ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

    ______________________________________                                        2.5. Coated granules                                                          a compound of the Tables                                                                            3%                                                      polyethylene glycol (mol. wt. 200)                                                                  3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

    ______________________________________                                        2.6. Suspension concentrate                                                   a compound of the Tables  40%                                                 ethylene glycol           10%                                                 nonylphenol polyethylene glycol ether                                                                    6%                                                 (15 mol of ethylene oxide)                                                    sodium lignosulfonate     10%                                                 carboxymethylcellulose     1%                                                 37% aqueous formaldehyde solution                                                                        0.2%                                               silicone oil in the form of a 75%                                                                        0.8%                                               aqueous emulsion                                                              water                     32%                                                 ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

3. BIOLOGICAL EXAMPLES Example 3.1 Action against Plasmopara viticola onvines

a) Residual protective action

Vine seedlings in the 4-5 leaf stage are sprayed with a spray mixture(0.02% active ingredient) prepared from a wettable powder formulation ofthe test compound. After 24 hours the treated plants are infected with asporangia suspension of the fungus. Fungus attack is evaluated afterincubation for 6 days at 95-100% relative humidity and 20° C.

b) Residual curative action

Vine seedlings in the 4-5 leaf stage are infected with a sporangiasuspension of the fungus. After incubation for 24 hours in a humiditychamber at 95-100% relative humidity and 20° C., the infected plants aredried and sprayed with a spray mixture (0.02% active ingredient)prepared from a wettable powder formulation of the test compound. Afterthe spray coating has dried, the treated plants are again placed in thehumidity chamber. Evaluation of fungus attack is made 6 days afterinfection.

Compounds of the Tables exhibit very good fungicidal activity againstPlasmopara viticola on vines, and in particular compounds nos. 1.6,1.13, 1.14, 1.16 and 1.30 inhibit fungus attack completely (0 to 5%residual attack). On the other hand, Plasmopara attack is 100% onuntreated and infected control plants.

Example 3.2 Action against Phytophthora on tomato plants

a) Residual protective action

After a cultivation period of 3 weeks, tomato plants are sprayed with aspray mixture (0.02% active ingredient) prepared from a wettable powderformulation of the test compound. After 24 hours the treated plants areinfected with a sporangia suspension of the fungus. The infected plantsare then incubated for 5 days at 90-100% relative humidity and 20° C.and then evaluated for fungus attack.

b) Systemic action

After a cultivation period of 3 weeks, a spray mixture (0.002% activeingredient, based on the volume of soil) prepared from a wettable powderformulation of the test compound is used to water tomato plants. Care istaken that the spray mixture does not come into contact with the partsof the plants above the soil. The treated plants are infected 48 hourslater with a sporangia suspension of the fungus. The infected plants arethen incubated for 5 days at 90-100% relative humidity and 20° C. andthen evaluated for fungus attack.

Compounds of the Tables exhibit a lasting effect (less than 20% fungusattack). Compounds Nos. 1.3, 1.6, 1.13, 1.14, 1.16, 1.30 and 1.58inhibit fungus attack almost completely (0 to 5% attack). On the otherhand, Phytophthora attack is 100% on untreated and infected controlplants.

Example 3.3 Action against Phytophthora on potato plants

a) Residual protective action

After a cultivation period of 3 weeks, 2- to 3-week old potato plants(Bintje variety) are sprayed with a spray mixture (0.02% activeingredient) prepared from a wettable powder formulation of the testcompound. The treated plants are infected 24 hours later with asporangia suspension of the fungus. The infected plants are thenincubated for 5 days at 90-100% relative humidity and 20° C. and thenevaluated for fungus attack.

b) Systemic action

After a cultivation period of 3 weeks, a spray mixture (0.002% activeingredient, based on the volume of soil) prepared from a wettable powderformulation of the test compound, is used to water 2- to 3-week oldpotato plants (Bintje variety). Care is taken that the spray mixturedoes not come into contact with the parts of the plants above the soil.The treated plants are infected 48 hours later with a sporangiasuspension of the fungus. The infected plants are then incubated for 5days at 90-100% relative humidity and 20° C. and then evaluated forfungus attack.

Compounds of the Tables exhibit a lasting effect (less than 20% fungusattack). Compounds nos. 1.6, 1.13, 1.14, 1.30 and 1.58 inhibit fungusattack almost completely (0 to 5% attack). On the other hand,Phytophthora attack is 100% on untreated and infected control plants.

What is claimed is:
 1. A compound of formula I ##STR18## wherein: R₁ ishydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy havingat least two identical or different halogen atoms, CF₃, nitro or thegroup N(R')R", wherein R' and R" are each independently of the other C₁-C₄ alkyl;R₂ is phenoxy or phenylthio each of which is unsubstituted ormono-to tri-substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy having at least two identical or different halogen atoms,cyano, nitro, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, phenyl, 2-phenylethynyl orby a further phenoxy radical that is unsubstituted or substituted byhalogen, C₁ -C₄ alkyl and/or by C₁ -C₄ alkoxy; or R₂ is phenoxy which issubstituted in the 3 and 4 positions by the radical --O--CH₂ --O--; R₃is alkyl, aryl or aralkyl having a maximum of 14 carbon atoms, theseradicals can be substituted by halogen, C₁ -C₄ alkyl and/or by nitro. 2.A compound according to claim 1 of formula I wherein: R₁ is hydrogen,halogen, C₁ -C₄ alkyl, methoxy, ethoxy, CF₃, NO₂, C₁ -C₂ haloalkoxyhaving at least two fluorine atoms, diethylamine or dimethylamine; andR₂ and R₃ are as defined for formula I.
 3. A compound according to claim2 of formula I wherein: R₁ is hydrogen, fluorine, chlorine, bromine,methyl, ethyl, methoxy, CF₃, NO₂, C₁ -C₂ haloalkoxy having at least 2fluorine atoms, or dimethylamine; and R₂ and R₃ are as defined forformula I.
 4. A compound according to claim 3 of formula I wherein: R₁is hydrogen, chlorine, bromine, methyl, methoxy, CF₃, NO₂,trifluoromethoxy, trifluorochloroethoxy, difluoromethoxy ordimethylamine; and R₂ and R₃ are as defined for formula I.
 5. A compoundaccording to claim 4 of formula I wherein: R1 is chlorine, methyl,methoxy, CF₃ or dimethylamine; and R₂ and R₃ are as defined for formulaI.
 6. A compound according to claim 1 of formula I wherein: R₂ isphenoxy or phenylthio each of which is unsubstituted or mono- ordi-substituted by fluorine, chlorine, bromine, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₂ haloalkoxy having at least 2 fluorine atoms, nitro,cyano, allyl, propargyl, 2-phenylethynyl or by a further phenoxy radicalthat is unsubstituted or substituted by fluorine, chlorine, bromine orby methyl; and R₁ and R₃ are as defined for formula I.
 7. A compoundaccording to claim 6 of formula I wherein: R₂ is phenoxy that isunsubstituted or substituted by fluorine, chlorine, bromine, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkoxy having at least 2 fluorineatoms, cyano, nitro, allyl, propargyl, 2-phenylethynyl or by a furtherphenoxy radical that is unsubstituted or substituted by fluorine,chlorine, bromine or by methyl; and R₁ and R₃ are as defined for formulaI.
 8. A compound according to claim 7 of formula I wherein: R₂ isphenylthio that is unsubstituted or substituted by fluorine, chlorine,C₁ -C₄ alkyl, C₁ -C₂ alkoxy, C₁ -C₂ haloalkoxy having at least 2fluorine atoms, nitro, allyl, propargyl or by 2-phenylethynyl; and R₁and R₃ are as defined for formula I.
 9. A compound according to claim 8of formula I wherein: R₂ is phenoxy that is unsubstituted or substitutedby chlorine, bromine, methyl, tert-butyl, methoxy, ethoxy,trifluoromethoxy, cyano, nitro, allyl, propargyl, 2-phenylethynyl or bya further phenoxy radical that is unsubstituted or substituted byfluorine, bromine or by methyl; and R₁ and R₃ are as defined for formulaI.
 10. A compound according to claim 1 of formula I wherein: R₃ is C₁-C₄ alkyl; C₁ -C₄ alkyl substituted by halogen; phenyl; phenylsubstituted by halogen, C₁ -C₄ alkyl and/or by nitro; benzyl; or benzylsubstituted by halogen, C₁ -C₄ alkyl and/or by nitro; and R₁ and R₂ areas defined for formula I.
 11. A compound according to claim 10 offormula I wherein: R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted byfluorine or by chlorine; phenyl; phenyl substituted by chlorine, methylor by nitro; benzyl; or benzyl substituted by chlorine, methyl or bynitro; and R₁ and R₂ are as defined for formula I.
 12. A compoundaccording to claim 1 of formula I wherein: R₁ is hydrogen, halogen, C₁-C₄ alkyl, methoxy, ethoxy, CF₃, NO₂, C₁ -C₂ haloalkoxy having at least2 fluorine and/or 2 chlorine atoms, diethylamine or dimethylamine;R₂ isphenoxy or phenylthio each of which is unsubstituted or mono-ordi-substituted by fluorine, chlorine, bromine, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₂ haloalkoxy having at least 2 fluorine atoms, cyano,nitro, allyl, propargyl, 2-phenylethynyl or by a further phenoxy radicalthat is unsubstituted or substituted by fluorine, chlorine, bromine orby methyl; and R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted by halogen;phenyl; phenyl substituted by halogen, C₁ -C₄ alkyl and/or by nitro;benzyl; or benzyl substituted by halogen, C₁ -C₄ alkyl and/or by nitro.13. A compound according to claim 12 of formula I wherein: R₁ ishydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, CF₃, NO₂,C₁ -C₂ haloalkoxy having at least 2 fluorine atoms, or dimethylamine;R₂is phenoxy that is unsubstituted or substituted by fluorine, chlorine,bromine, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkoxy having at least2 fluorine atoms, cyano, nitro, allyl, propargyl, 2-phenylethynyl or bya further phenoxy radical that is unsubstituted or substituted byfluorine, bromine or by methyl; and R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkylsubstututed by fluorine or by chlorine; phenyl; phenyl substituted bychlorine, methyl or by nitro; benzyl; or benzyl substituted by chlorine,methyl or by nitro.
 14. A compound according to claim 13 of formula Iwherein: R₁ is hydrogen, chlorine, bromine, methyl, methoxy, CF₃, NO₂,trifluoromethoxy, trifluorochloroethoxy, difluoromethoxy ordimethylamine;R₂ is phenylthio that is unsubstituted or substituted byfluorine, chlorine, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, C₁ -C₂ haloalkoxyhaving at least 2 fluorine atoms, nitro, allyl, propargyl or by2-phenylethynyl; and R₃ is C₁ -C₄ alkyl; C₁ -C₄ alkyl substituted byfluorine or by chlorine; phenyl; phenyl substituted by chlorine, methylor by nitro; benzyl; or benzyl substituted by chlorine, methyl or bynitro.
 15. A compound according to claim 14 of formula I wherein: R₁ ischlorine, methyl, methoxy, CF₃ or dimethylamine;R₂ is phenoxy that isunsubstituted or substituted by chlorine, bromine, methyl, tert-butyl,methoxy, ethoxy, trifluoromethoxy, cyano, nitro, allyl, propargyl,2-phenylethynyl or by a further phenoxy radical that is unsubstituted orsubstituted by fluorine, bromine or by methyl; and R₃ is C₁ -C₄ alkyl;C₁ -C₄ alkyl substituted by fluorine or by chlorine; phenyl; phenylsubstituted by chlorine, methyl or by nitro; benzyl; or benzylsubstituted by chlorine, methyl or by nitro.
 16. A compound of formula Iaccording to claim 1 selected from the group consistingof:1-N-methanesulfonyl-5-chloro-6-phenoxy-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(2-chlorophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(4-chlorophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(2,4-dibromophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(2-fluorophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(4-ethoxyphenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-phenoxy-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(2-chlorophenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(4-chlorophenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(2,4-dibromophenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(2-fluorophenoxy)-benzotriazole; and3-N-methanesulfonyl-5-chloro-6-(4-ethoxyphenoxy)-benzotriazole;andmixtures of the 1-N- and 3-N-substituted structural isomers.
 17. Acomposition for controlling or preventing an attack by harmfulmicroorganisms, which comprises a microbicidally effective amount of acompound or mixture of compounds of formula I ##STR19## wherein: R₁ ishydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy havingat least two identical or different halogen atoms, CF₃, nitro or thegroup N(R')R", wherein R' and R" are each independently of the other C₁-C₄ alkyl;R₂ is phenoxy or phenylthio each of which is unsubstituted ormono-to tri-substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy having at least two identical or different halogen atoms.cyano, nitro, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, phenyl, 2-phenylethynyl orby a further phenoxy radical that is unsubstituted or substituted byhalogen, C₁ -C₄ alkyl and/or by C₁ -C₄ alkoxy; or R₂ is phenoxy which issubstituted in the 3 and 4 positions by the radical --O--CH₂ --O--; R₃is alkyl, aryl or aralkyl having a maximum of 14 carbon atoms, theseradicals can be substituted by halogen, C₁ -C₄ alkyl and/or bynitro;together with a suitable carrier.
 18. A composition of claim 17wherein R₁ is hydrogen, halogen, C₁ -C₄ alkyl, methoxy, ethoxy, CF₃,NO₂, C₁ -C₂ haloalkoxy having at least two fluorine atoms, diethylamineor dimethylamine.
 19. A composition of claim 17 whereinR₁ is hydrogen,halogen, C₁ -C₄ alkyl, methoxy, ethoxy, CF₃, NO₂, C₁ -C₂ haloalkoxyhaving at least 2 fluorine and/or 2 chlorine atoms, diethylamine ordimethylamine; R₂ is phenoxy or phenylthio each of which isunsubstituted or mono-or di-substituted by fluorine, chlorine, bromine,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₂ haloalkoxy having at least 2fluorine atoms, cyano, nitro, allyl, propargyl, 2-phenylethynyl or by afurther phenoxy radical that is unsubstituted or substituted byfluorine, chlorine, bromine or by methyl; and R₃ is C₁ -C₄ alkyl; C₁ -C₄alkyl substituted by halogen; phenyl; phenyl substituted by halogen, C₁-C₄ alkyl and/or by nitro; benzyl; or benzyl substituted by halogen, C₁-C₄ alkyl and/or by nitro.
 20. A composition of claim 17 wherein thecompound of formula I is selected from the group consistingof1-N-methanesulfonyl-5-chloro-6-phenoxy-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(2-chlorophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(4-chlorophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(2,4-dibromophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(2-fluorophenoxy)-benzotriazole;1-N-methanesulfonyl-5-chloro-6-(4-ethoxyphenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-phenoxy-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(2-chlorophenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(4-chlorophenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(2,4-dibromophenoxy)-benzotriazole;3-N-methanesulfonyl-5-chloro-6-(2-fluorophenoxy)-benzotriazole; and3-N-methanesulfonyl-5-chloro-6-(4-ethoxyphenoxy)-benzotriazole;andmixtures of the 1-N- and 3-N-substituted structural isomers.
 21. Amethod of controlling or preventing an attack on cultivated plants byphytopathogenic microorganisms, which comprises applying to the plants,parts of plants or the locus thereof, a microbicidally effective amountof a compound or mixture of compounds of formula I ##STR20## wherein: R₁is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxyhaving at least two identical or different halogen atoms, CF₃, nitro orthe group N(R')R", wherein R' and R" are each independently of the otherC₁ -C₄ alkyl;R₂ is phenoxy or phenylthio each of which is unsubstitutedor mono- to tri-substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkoxy having at least two identical or different halogen atoms,cyano, nitro, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, phenyl, 2-phenylethynyl orby a further phenoxy radical that is unsubstituted or substituted byhalogen, C₁ -C₄ alkyl and/or by C₁ -C₄ alkoxy; or R₂ is phenoxy which issubstituted in the 3 and 4 positions by the radical --O--CH₂ --O--; R₃is alkyl, aryl or aralkyl having a maximum of 14 carbon atoms, theseradicals can be substituted by halogen, C₁ -C₄ alkyl and/or by nitro.22. A method of claim 21 wherein R₁ is hydrogen, halogen, C₁ -C₄ alkyl,methoxy, ethoxy, CF₃, NO₂, C₁ -C₂ haloalkoxy having at least twofluorine atoms, diethylamine or dimethylamine.
 23. A method according toclaim 21, wherein phytopathogenic fungi are controlled.
 24. A methodaccording to claim 21, wherein the phytopathogenic fungi are Oomycetes.25. A method according to claim 24, wherein the Oomycetes are thespecies Plasmopara and Phytophthora.